Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
` ~ ~ 3~4~ FN 915,3]4
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POLYESTER-FILM ~ACKED MAGNETIC RECORDING TAPE HAVING
EPOXY SUBBING LAYER
The backing for most magnetic recording tapes is
biaxially-oriented polyester film, especially polyethylene
terephthalate. When used as a magnetic recording tape
backing, low-molecular~weight organic components of
polyester film tend ~o migrate to and crystallize at the
surface of the magnetizable coating. Such components
gradually transfer to and build up on the recording/
playback heads to cause an undesirable loss of signal.
This problem is aggravated if solvent is used in applying
the magnetizable coating, because the solvent tends to
extract low-molecular-weight components of the polyester
film into the magnetizable coating.
.:,
In a magnetic recording tape having a backside
coating, the low-molecular-weight components also tend to
be solvent-extracted into and to migrate to the surface of
that coating. During storage of the tape in roll form,
they tend to crystallize on the surEace o~ the magnetizable
coating as well as on the backside coating.
The present invention concerns magnetic recording
tape having a bia~ially-oriented polyester film backing, a
magnetizable coating and a subbing layer between the magnetiz-
able coating and film backing, characterized by the feature
that the subbiny layer comprises a cationically polymerized
epoxy resin. The subbing layer, which virtually eliminates
the problem of extraction and migration,can be applied at a
~,
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temperature involving no danger of distorting the film.
Preferably the epoxy resin and a photoinitiator
of cationic polymerization are together coated onto the
polyester film from a solvent which quickly volatiliæes,
whereupon the coating can be exposed to ultraviolet light
which decomposes the photoinitiator to generate a fast-
acting cationic curing agent for the epoxy resin. Usually
the epoxy resin becomes cured to a tack-free state simply
by brief exposure to the ultraviolet light, but if not, it
should be cured further by heat prior to application of
the magnetizable coating of the recording tape. In addi-
tion to its barrier function, the subbing layer tends to
promote adhesion and it also enhances the smoothness of
the magnetizable coating, especially when the film has a
roughness such as is often imparted by a slip agent.
Subbing layers formed from epoxy resins which are viscous
liquids at room temperature are especially effective in
the latter respect.
The novel barrier is also useful as a subbing
layer for the backside coating, if any, of magnetic
recording tape. In such use, it inhibits low-molecular-
weight components from reaching the surface of the
magnetizable coating through the backside coating.
In manufacturing the magnetic recording tape,
the novel subbing layer is conveniently applied in-line
with the subseguent magnetizable or backside coating,
since the subbing layer can be cured to a tack-free state
~:~3~
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within a few seconds. The subbing layer is immediately
capable of virtually prohibiting the extraction of
low-molecular-weight components from the film backing by
the solvents used in applying the magnetizable or backside
- 5 coating.
Extensive experimentation indicates the utility
of any epoxy resin that can be cationically polymerized to
; a strong, tough thermoset state. Particularly preferred
are epoxy resins which can be cationically polymerized at
fast rates such as the cycloaliphatic epoxy resins. Also
useful in this respect are the condensation products of
bi~phenol A and epichlorohydrin and the epoxidized novolak
resins.
To create the most effective barrier against the
migration of low-molecular-weight components, the epoxy
resin should have at least about two l,2-epoxy groups per
molecule and an epoxide equivalent weight of less than 300
in order to provide a rather tightly crosslinked network.
In amounts up to about 10% by weight of the total polymer-
izable com~osition, a polyol such as triethylene glycoltends to enhance the rate of polymerizing the epoxy resin.
However, at more than 30% by weight of the polymerizable
composition, a polyol tends to reduce the effectiveness of
the cured layer as a barrier against migration of the
low-molecular-weight components~ At least up to 50% by
weight of the polymerizable composition may comprise a
monofunctional epoxide such as an alkyl glycidyl ether
-4-
having an epoxide equivalent weight of less than 300.
The cationically polymerized epoxy resin layer
should provide an effective barrier against the solvent
`- extraction and migration of low-molecular-weight
components of the polyester film backing at virtually
mono-molecular thickness. However, to ensure against
discontinuities, a cured thickness of at least 0.1
micrometer is preferred. Thicknesses exceeding about five
micrOmeters may be economically wasteful.
Preferred as photoinitiators are the triaryl-
sulfonium salts similar to those disclosed in the above-
cited J. Radiat. Curing, 5 (1) of Jan. 1978, pages 2-17,
especially the triarylsulfonium salts of HBF4, HPF6, HAsF6
and HSbF6. Also particularly useful are diaryliodonium
salts such as are referenced in that publication and
diazonium salts disclosed in U. S. Patent No. 3,708,296.
Even though they provide very fast cationic polymerization
of the epoxy resin, blends of these photoinitiators with
epoxy resin can be stored in darkness at ordinary room
temperature for more than a year without significant
reaction.
In the absence of a photoinitiator, cationic
polymerization of epoxy resin can be carried out at
temperatures of 70-105C, with the epoxy resin becoming
tack-free at that temperature within two minutes. A
mixture of dibutyl diphenyl tin, 2,6-dimethylaniline and
hydrogen hexafluoro antimonate(V) hexahydrate is suitable
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for this purpose. However, it may be necessary to prepare
a fresh coating composition at least once for each ~-hour
shift.
of the following tests the first three were
employed to evaluate effectiveness of barriers against the
migration of low-molecular-weight components of biaxially-
oriented polyethylene terephthalate film under conditions
simulating accelerated aging.
Surface Barrier Test
A piece of polyester film having a surface
barrier is placed in an oven at 140C for 24 hours, and
the surface of the barrier is then examined at 200X
magnification under polarized light. The volume of
low-molecular-weight components which crystallize in a
square centimeter of the surface of the barrier is
calculated by estimating the dia~eter of each observable
crystal and assuming it has a half-sphere shape. This
test provides a preliminary indication of the effec-
tiveness of a barrier as a subbing layer in a magnetic
recording tape.
Subbing Layer Barrier Test
Moderate pressure is applied to a piece of
polyester-backed magnetic recording tape having a subbing
layer beneath the magne~izable coating with the
magnetizable coating in contact with a glass slide etched
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to provide seeding points. After 24 hours at 140C, the
surface of the magnetizable coating is examined, and the
- volume of observable crystals is calculated in the same
way as in the Surface Barrier Test.
Ma~netic Recording Tape Test
Two pieces of a magnetic recording tape are held
at 140C for 24 hours while the magnetizable coating of
one piece is under moderate pressure against the backside
coating of the other. The surface of the magnetizable
coating is then examined as in the Surface Barrier Test.
Surface Extractables Test
For five minutes at room temperature, 25 ml of
chloroform is in contact With 25 cm2 of one face of a
polyester film which may have a surface barrier to be
tested. The chloroform is then analyzed using standard
liquid chromatographic techniques to measure the amount of
extracted material having a molecular weight of 576 when
the polyester film is polyethylene t.erephthate film.
since the predominant low-molecular-weight component of
polyethylene terephthalate film is trimer having a
molecular weight of 576, the test accurately indicates the
degree of extraction of low-molecular-weight components.
This test may be used to provide a preliminary evaluation
of the effectiveness of a barrier against solvent
extractiOn of low-molecular-weight components of a
1~,3~,t~
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polyester film upon subsequent application of the
.~ magnetizable or backing coating.
Preliminary Testiny
A variety of surface barriers were applied to
biaxially-oriented polyethylene terephthalate film 25
micrometers in thickness. In each case, a 10% solution of
an epoxy resin composition was applied with a knife
coater. Some of the compositions contained diluent.
Each compo~sition employed 2 parts by weight of triaryl-
sulfonium hexafluoroantimonate per 100 parts of the epoxyresin. The dried coatings were exposed to two medium-
pressure mercury ultraviolet lamps at a distance of about
6 cm for an expo~ure of 5.3 watts~m2/min. to provide cured
surface barriers about 3/4 micrometer in thickness. These
were compared by the Surface Barrier Test to an identical
polyester film having no coating, with the following
results:
Epoxy Resin Diluent Volume of Crystals
Name _ __ _ Parts
None None 10-6
ERL 4221 None <lo-14
do Polytetramethylene 10 lo-l3
glycol (MW 650)
do do 20 10-9
do Triethylene glycol 10 <10-14
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- do do 20 <1o-14
do do 30 10-7
do Butyl glycidyl ether 20 <10-14
do do 50 <lo-l4
ERL 4234 None <10-14
ERL 4206 do <lo-14
ERL 4289 do 10-9
D.E.N.431 do 10-10
D.E.N.438 do 10-9
"Epon" 828 do 1o-12
do Polytetramethylene 10 1o-12
glycol (MW 650~
do do 20 10-8
Each of the above ERL epoxy resins is a cycloaliphatic
epoxy resin, the epoxide equivalent weights of which are;
Epoxide equivalent weight
ERL 4221 131-143
ERL 4234 133-154
ERL 4206 74-78
ERL 4289 205 216
; The D.E.N. 431 and 438 resins are condensation products of
epichlorohydrin and novolak resin and have epoxide
equivalent weights of 172-179 and 176-181, respectively.
"Epon" 828 is a condensation product of epichlorohydrin
and bisphenol A having an epoxide equivalent weight of
180-195.
3~
g
To biaxially-oriented polyester film 25 micro-
meters in thickness were applied solutions containing 2
parts by weight of triarylsulfonium hexafluoroantimonate
per 100 parts epoxy resin. The dried coatings were
exposed to two medium-pressure mercury lamps for an
exposure of 5.3 watts/m2/min. to provide cured surface
barriers of about 1/2 micrometer in thickness. Samples
were compared in the Surface Extractables Test to an
identical polyester film having no barrier with the
following results.
Barrier Composition Extracted Trimer
ERL 4221/Polytetramethylene glycol, Non-detectable
MW 650 (90/10)
ERL 4221/Polypropylene oxide based Non-detectable
triol, MW 440 (90/10)
No barrier 3600 ~g/cm2
Comparative Exam~_e A
A magnetic dispersion was made by first
premixing the following in a kettle for 2 hours.
20 Material Parts by Weight
25% solution of polyurethane elastomer13.30
in methyl ethyl ketone
30% solution of phenoxy resin in methyl 3.00
ethyl ketone
25 75% solu~ion of dispersant, in toluene 5.30
Additional dispersant 1.00
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Lubricants 2.75
Additional solvents 142.90
Acicular gamma-Fe203 100.00
Carbon black 1.33
5 Aluminum oxide 3.00
The polyurethane elastomer was a high-molecular-
weight polyester-polyurethane polymer synthesized from
neopentyl glycol, poly-epsilon-caprolactone diol and
p,p'-diphenylmethane diisocyanate. The phenoxy resin was
a thermoplastic copolymer of equivalent amounts of
bisphenol A and epichlorohydrin, and was of the type sold
as PKHH by Union Carbide Corp. The acicular iron oxide
was modified with cobalt as disclosed in U. S. Patent No.
3,725,126.
After milling the resultant slurry in a sandmill
for 16-20 hours, the following were added:
Parts by weight
25% solution of the polyurethane elastomer 33.30
30% solution of the phenoxy resin 8.30
with continued milling until a smooth dispersion was
obtained. Solvents were added to adjust to 40% solids, and
immediately prior to coating, one part polymethylene
polyphenyl isocyanate was added per 100 parts by weight of
solids as a cross-linking agent. A gravure roll was
employed to coat this dispersion onto a biaxially-oriented
polyethylene terephthalate polyester film 20 micrometers
--ll--
in ~hickness, and the wet coa~ing was subjected to a flat
magnetic field to align the acicular particles in the
lengthwise direction of the film. The dry thickness of
the magnetizable coating of the resultant magnetic
recording tape was 6.1 micrometers.
To provide good winding characteristics, the
backside of the tape was coated with a dispersion of
conductive carbon black in a binder similar to that of the
magnetizable coating.
_a~
A magnetic recording tape identical to that of
Comparative Example A was made except that a subbing layer
was applied to the face of the film to which the
magnetizable coating was subsequently applied. The
subbing layer was made from a solution of:
Parts by weight
Epoxy resin (ERL 4221) 89
TriethyLene glycol
Triarylsulfonium hexafluorophosphate 2
Surfactant
Methyl ethyl ketone (MEK) 566
Using a gravure roll, the solution was applied
to the polyethylene terephthalate film. After 5-10
seconds during which the solvent quickly evaporated~ the
still-tacky coating was passed about 6 cm beneath a series
~31~
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of four medium-pressure ultraviolet mercury lamps which
extended beyond the edges of the film. The lamps provided
an exposure of 5.3 watts/m2/min., thus adequately curing
the epoxy resin to permit the magnetizable coating to be
applied in-line. The thickness of the cured epoxy
subbing layer was about 3/4 micrometer.
Example 2
A magnetic recording tape was prepared in the
same way as in Comparative Example A except that the
magnetizable coating had a different binder and there was
a cationically polymerized epoxy resin barrier layer
- between the backing film and the backside coating. The
magnetizable dispersion, which was coated directly onto
the backing film, comprised:
Parts by weight
Acicular cobalt-modified iron
oxide particles 100.0
Polyurethane elastomer 9.3
Polymethylene polyphenyl isocyanat.e1.3
20 Polyvinyl chloride/acetate copolymer6.6
Dispersant 6.5
Lubricants 2.5
Aluminum oxide 2.0
The subbing layer which had a thickness of about 1/2
micrometer was prepared from:
~13-
Parts by_weight
- Epoxy resin (ERL 4221) 89.0
polypropylene oxide based triol,
~W 440 9~2
Triarylsulfonium hexafluoroantimonate 1.8
An ultraviolet lamp exposure of 1.5 watts/m2/min. cured
the subbing layer to a tack-free state to permit the back-
side coating to be applied in-line with the application of
the barrier.
Example_3
A magnetic recording tape was prepared which was
identical to that of Example 2 except that the same
subbing layer was also employed between the backing film
and the magnetizable coating~ and the thickness of each
barrier layer was about 1/2 micrometer.
Example 4
A magnetic recording tape was prepared identical
to Example 3 except both subbing layers were prepared from
a 10% solution in MEK of the following:
Parts by weight
Epoxy resin (ERL 4221~ 90
Poly tetramethylene glycol 10
(MW 6S0)
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To this was added 1 part by weight of a catalyst solution
comprisin~ 2.38 g of 2,6-dimethylaniline, 3.87 g of
dibutyl diphenyl tinl 3.45 g of hydrogen hexafluoro-
antimonate(V) hexahydrate and 40.3 g of MEK. The catalyst
solution was allowed to stand overnight before use. The
subbing layers were not exposed to ultraviolet light but
were thermally cured at 105C for one minute.
The tapes of Comparative Example A and Examples
1-3 were tested on a helical-scan video recorder for
1) RF output of a 9.0 MHz carrier;
2) Broadband signal-to-noise ratio;
3) Color signal-to-noise ratio.
Results in comparison to the tape of Comparative Example A
were as follows:
Tape of Examples _ 2 3_
RF output -0.2 db -0.1 db +0.4 db
Signal-to-noise +0.3 db ~0.5 db +1.2 db
Color signal-to-noise +3.4 db -0.6 db +2.0 db
While the tapes of Examples 2 and 3 are not precisely
comparable to that of Comparative Example A because of
their binder differences, the improvements in color
signal-to-noise of Example 1 versus Comparative Example A
and of Example 3 versus Example 2 can be attributed to a
smoother recording surface due to the underlying barrier
layer.
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The surface roughness of the polyester film base
of Comparative Example A and Examples 1-4 had been
measured using a Bendix "Proficorder" Model No. 5 equipped
with a 2.5-micrometer stylus. Its peak-to-peak roughness
was 0.25 micrometer, whereas that of the subbing layers of
- Examples 1-3 was 0.05 micrometer.
The tapes of the examples were also tested with
the following results:
Volume of Crystals
(cm3/cmZ)
Example
A 1 2 3 4
_ _ _ _ _ _ _ _ _
Subbing Layer
Barrier Test 7x10-7 * 4x10-8 * *
Magnetic Recording
Tape Test 5x10-7 2x10-7 lx10-8 * *
* indicates < 10-14
Although the observed volume of cryst,als reported above
may seem small, any amount exceeding 10-9 cm3/cm2 is
unsatisfactory for most uses, and a value of less than
10-12 is necessary for many uses. The difference in
results of these two tests on the tapes of Example 1 is
attributed to crystallization on the surface of the
magnetizable layer of low--molecular-weight components
which exuded through the backside coating.
~r ~L 3 ~
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References herein to polyester-backed magnetic
recording tape are intended to include all forms such as
disks, cards and sheets.
